CN104169359A - Electron beam curable resin composition, resin frame for reflectors, reflector, semiconductor light emitting device, and method for producing molded body - Google Patents

Electron beam curable resin composition, resin frame for reflectors, reflector, semiconductor light emitting device, and method for producing molded body Download PDF

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Publication number
CN104169359A
CN104169359A CN201380014798.9A CN201380014798A CN104169359A CN 104169359 A CN104169359 A CN 104169359A CN 201380014798 A CN201380014798 A CN 201380014798A CN 104169359 A CN104169359 A CN 104169359A
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CN
China
Prior art keywords
resin combination
allyl
reverberator
treatment agent
crosslinking treatment
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CN201380014798.9A
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Chinese (zh)
Inventor
坂井俊之
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Publication of CN104169359A publication Critical patent/CN104169359A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/08—Conditioning or physical treatment of the material to be shaped by using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2035/00—Use of polymers of unsaturated polycarboxylic acids or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2039/00—Use of polymers with unsaturated aliphatic radicals and with a nitrogen or a heterocyclic ring containing nitrogen in a side chain or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2012/00—Frames
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
    • H01L33/46—Reflective coating, e.g. dielectric Bragg reflector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture

Abstract

The present invention provides an electron beam curable resin composition; a resin frame for reflectors, which uses the resin composition; a reflector; a semiconductor light emitting device; and a molding method which uses the resin composition. The electron beam curable resin composition contains a polymethylpentene and a crosslinking agent. The crosslinking agent has a saturated or unsaturated ring structure, and at least one atom among the atoms constituting at least one ring thereof is bonded to an allyl substituent that is selected from among an allyl group, a methallyl group, an allyl group having an intervening linking group and a methallyl group having an intervening linking group. The crosslinking agent has a molecular weight of 1,000 or less.

Description

Electrocuring resin combination, the manufacture method of resinous framework, reverberator, semiconductor light-emitting apparatus and molding for reverberator
Technical field
The present invention relates to a kind of electrocuring resin combination, the manufacture method of resinous framework, reverberator, semiconductor light-emitting apparatus and molding for reverberator.
Background technology
At present, method as mounting electronic device on substrate, employing, after the place of stipulating is in advance with temporary transient fixedly electron device on the substrate of scolder, utilizes the means such as infrared rays, hot blast this substrate to be heated to the method (backflow welding method) that makes melt solder fix electron device.By the method, can improve the packing density of the electron device of substrate surface.
Yet the thermotolerance of the electron device using is at present insufficient, particularly in utilizing the Reflow Soldering operation of infrared heating, there is the problems such as the temperature part of piece surface uprises, more excellent resin combination and the electron device of expectation thermotolerance.
In addition, as the LED element of one of semiconductor light-emitting apparatus, due to the small-sized and long lifetime, economize on electricity property is excellent, therefore, is widely used as the light source of pilot lamp etc.And, in recent years, owing to can manufacturing more at an easy rate the higher LED element of brightness, therefore, study the instead utilization of the light source of luminescent lamp and incandescent-lamp bulb.In the situation that be applied to such light source, in order to obtain larger illumination, the surface mounting LED packaged pieces that use more, that is: at a plurality of LED elements of the upper configuration of the metal substrates such as aluminium (LED mounting substrate), in the surrounding of each LED element, set and make luminous reflectance to the mode of the reverberator (tamper) of prescribed direction.
But, due to LED element when luminous with heat release, therefore, the LED means of illumination of such mode makes reverberator deteriorated because the temperature of LED element when luminous rises, and because its reflectivity reduces, brightness is reduced, and causes the short life of LED element etc.Therefore, reverberator is required to thermotolerance.
In order to respond above-mentioned stable on heating requirement, a kind of polymer composition of the reverberator for photodiode is disclosed in patent documentation 1, particularly, a kind of polymer composition that contains polyphthalamide, carbon black, titanium dioxide, glass fibre and antioxidant is disclosed.And, said composition is measured to the reflectivity after thermal ageing, compare with the polymer composition that does not contain carbon black, show that said composition can obtain good reflectivity, xanthochromia is also few.
In addition, disclose a kind of Thermocurable luminous reflectance resin combination in patent documentation 2, it is for combining the optical semiconductor device of optical semiconductor and fluor equiwavelength transfer equipment.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2006-503160 communique
Patent documentation 2: TOHKEMY 2009-149845 communique
Summary of the invention
Invent problem to be solved
But, although the Thermocurable luminous reflectance of recording in patent documentation 2 is verified under so more practical condition at 150 ℃, 500 hours by the heat ageing test of resin combination, but curring time is 90 seconds, longer than thermoplastic resin, in addition, due to as after fixing, need 2 hours at 150 ℃, therefore, productivity existing problems.
The heat ageing test of the polymer composition of recording in patent documentation 1 is the evaluation of 170 ℃, 3 hours such short period of time, and it is not yet clear and definite whether the heat-resisting weather resistance under the practical condition of longer time can obtain good result.
According to above content, the object of the invention is to, provide a kind of and in Reflow Soldering operation, show excellent thermotolerance, and in the situation that making the moldinies such as reverberator, also can bring into play excellent stable on heating electrocuring resin combination, use resinous framework, reverberator, the semiconductor light-emitting apparatus for reverberator of this resin combination and use the manufacturing process of this resin combination.
For the method for dealing with problems
The inventor etc. concentrate on studies to achieve these goals, found that, can realize by following invention this object.That is, the present invention is as described below.
[1] an electrocuring resin combination, it contains polymethylpentene and crosslinking Treatment agent,
Described crosslinking Treatment agent has saturated or undersaturated ring structure, and the arbitrary allyl class substituting group bonding in the methacrylic that forms at least 1 atom in the atom of at least 1 ring and allyl group, methacrylic, the allyl group being connected by linking group and connect by linking group, the molecular weight of described crosslinking Treatment agent is below 1000.
[2] the electrocuring resin combination according to [1], wherein, form at least 2 atoms in the atom of 1 ring of described crosslinking Treatment agent respectively independently with described allyl class substituting group bonding.
[3] according to the electrocuring resin combination [2] described, wherein, the ring of described crosslinking Treatment agent is 6 rings, and form at least 2 atoms in the atom of this ring respectively independently with described allyl class substituting group bonding, atom, other allyl class substituting group and a position atomic linkage with respect to 1 allyl class substituting group institute bonding.
[4] according to the electrocuring resin combination described in any one in [1]～[3], wherein, described crosslinking Treatment agent is represented by following formula (1).
(in formula (1), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.)
[5] according to the electrocuring resin combination described in any one in [1]～[3], wherein, described crosslinking Treatment agent is represented by following formula (2).
(in formula (2), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.)
[6] according to the electrocuring resin combination described in any one in [1]～[5], wherein, with respect to polymethylpentene 100 mass parts, be combined with the described crosslinking Treatment agent of 0.1～15 mass parts.
[7] according to the electrocuring resin combination described in any one in [1]～[6], it contains white pigment.
[8], according to the electrocuring resin combination [7] described, it contains the inorganic particulate beyond described white pigment.
[9], according to the electrocuring resin combination [8] described, wherein, the inorganic particulate beyond described white pigment is spheroidal fused silicon dioxide granule and/or special crosssection glass fibre.
[10] a reverberator resinous framework, the cured article that it contains the electrocuring resin combination described in any one in [1]～[9].
[11] according to the reverberator resinous framework [10] described, its thickness is 0.1～3.0mm.
[12] reverberator, the cured article of its electrocuring resin combination described in any one in [1]～[9] is made.
[13] a kind of semiconductor light-emitting apparatus, it has optical semiconductor and reverberator on substrate, described reverberator is arranged at this optical semiconductor around, and to prescribed direction, the cured article of at least a portion of the light reflection surface of described reverberator electrocuring resin combination described in any one in [1]～[9] is made by the luminous reflectance from this optical semiconductor.
[14] manufacture method for molding, it comprises: injection molded operation, at 20～100 ℃ of 200～400 ℃ of injection temperatures, die temperature to [1]～[9] in electrocuring resin combination described in any one carry out injection molded; With electron beam irradiation operation, before or after injection molded operation, implement electron beam irradiation and process.
The effect of invention
According to the present invention, can provide a kind of and show excellent thermotolerance in Reflow Soldering operation, even and if also can bring into play excellent stable on heating electrocuring resin combination in the situation that making the moldinies such as reverberator, use resinous framework, reverberator, the semiconductor light-emitting apparatus for reverberator of this resin combination and use the manufacturing process of this resin combination.
Accompanying drawing explanation
Fig. 1 means the summary sectional view of an example of semiconductor light-emitting apparatus of the present invention.
Fig. 2 means the summary sectional view of an example of semiconductor light-emitting apparatus of the present invention.
Nomenclature
10 optical semiconductors
12 reverberators
14 substrates
16 lead-in wires
18 lens
Embodiment
[1. electrocuring resin combination]
Electrocuring resin combination of the present invention contains polymethylpentene and specific crosslinking Treatment agent.
Polymethylpentene is because specific refractory power is 1.46, very approaching with the specific refractory power of silicon dioxide granule, therefore, even also can suppress the obstruction of the optical characteristics such as transmissivity or reflectivity when mixing.If consider this point, can be preferably used as for example reverberator of semiconductor light-emitting apparatus.
But, sometimes insufficient with respect to the thermotolerance in Reflow Soldering operation.For this problem, the present invention, by contain specific crosslinking Treatment agent irradiating electron beam in polymethylpentene, also can bring into play sufficient stable on heating resin combination even if can be made in Reflow Soldering operation.Thus, when making reverberator, also can prevent the distortion of the reverberator that the melting because of resin causes.
The fusing point of polymethylpentene is up to 232 ℃, even be that 280 ℃ of left and right can not decomposed yet in processing temperature, having decomposition temperature is 300 ℃ of characteristics that left and right is such.On the other hand, owing to thering is organo-peroxide or the Photoepolymerizationinitiater initiater of such characteristic, conventionally do not exist, therefore, cannot utilize the crosslinked of organo-peroxide or utilize the crosslinked of UV-light.
In addition, even for example, to polymethylpentene irradiating electron beam (, absorbed dose: 200kGy), also can carry out the cut-out of molecular chain in crosslinked, therefore, resin monomer is difficult to cause effectively crosslinked.But, by containing crosslinking Treatment agent of the present invention, by electron beam irradiation, effectively cause crosslinking reaction, therefore, even if also can prevent the distortion that the dissolving because of resin causes in Reflow Soldering operation.
Such crosslinking Treatment agent has saturated or undersaturated ring structure, there is at least 1 atom in the atom of at least 1 ring of formation and allyl group, methacrylic, the allyl group being connected by linking group and the methacrylic that connects by linking group in the structure that forms of arbitrary allyl class substituting group bonding.By containing the crosslinking Treatment agent with this structure, can bring into play good electrocuring, form and there is excellent stable on heating resin combination.
As saturated or undersaturated ring structure, can enumerate: cyclic rings, heterocycle, aromatic nucleus etc.The atomicity that forms ring structure is preferably 3～12, and more preferably 5～8,6 rings more preferably.
In addition, the molecular weight of crosslinking Treatment agent of the present invention is below 1000, is preferably below 500, more preferably below 300.If molecular weight surpasses 1000, the dispersed variation in resin combination, even if irradiating electron beam also cannot cause effective crosslinking reaction.
In addition, the number of ring structure is preferably 1～3, and more preferably 1 or 2, more preferably 1.
At this, as the linking group in crosslinking Treatment agent of the present invention, can enumerate: ester bond, ehter bond, alkylidene group, (mixing) arylidene etc.Form in the atom of ring not atom with allyl class substituting group bonding and be with the state of the bonding such as hydrogen, oxygen, nitrogen or with the state of various substituting group bondings.
Crosslinking Treatment agent of the present invention be preferably formed at least 2 atoms in the atom of 1 ring of this crosslinking Treatment agent respectively independently with allyl class substituting group bonding.In addition, in the situation that ring structure is 6 ring, be preferably formed at least 2 atoms in the atom of this ring respectively independently with allyl class substituting group bonding, and with respect to atom, other allyl class substituting group and a position atomic linkage of 1 allyl class substituting group institute bonding.
And then crosslinking Treatment agent of the present invention is preferably represented by following formula (1) or (2).
(in formula (1), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.)
(in formula (2), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.)
As the crosslinking Treatment agent shown in above-mentioned formula (1), can enumerate: cyanacrylate, methyl diallyl isocyanuric acid ester, diallyl list glycidyl isocyanuric acid, monoene propyl group diglycidyl isocyanuric acid ester, isocyanuric acid trimethylammonium allyl ester etc.
As the crosslinking Treatment agent shown in above-mentioned formula (2), can enumerate Phthalic acid, diallyl ester, diallyl isophthalate etc.
Crosslinking Treatment agent of the present invention preferably coordinates 0.1～15 mass parts with respect to polymethylpentene 100 mass parts, more preferably coordinates 0.5～5 mass parts, further preferably coordinates 0.1～2.5 mass parts.By coordinating 0.1～15 mass parts, can not ooze out and effectively be cross-linked.
As polymethylpentene resin, the homopolymer of preferred 4-methylpentene-1, but also can be the multipolymer of 4-methylpentene-1 and the alpha-olefin of other alpha-olefin, carbonatomss 2～20 such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-octadecylene, 1-icosa alkene, 3-methyl-1-butene, 3-Methyl-1-pentene, the multipolymer that 4-methylpentene-1 that also can be to contain 90 % by mole of above 4-methyl-1-pentenes is main body.
The weight-average molecular weight Mw of the polystyrene conversion that the molecular weight of the homopolymer of 4-methylpentene-1 records by gel permeation chromatography is preferably more than 1,000, is particularly preferably more than 5,000.
In electrocuring resin combination of the present invention, preferably contain white pigment.By containing white pigment, be available for the purposes of reverberator etc.In addition, preferably contain white pigment inorganic particulate in addition.As the inorganic particulate beyond this white pigment, can enumerate: spheroidal fused silicon dioxide granule, special crosssection glass fibre, other glass fibre etc., preferred spherical fused silica particle and/or special crosssection glass fibre.Such electrocuring resin combination is specially adapted to reverberator.
As white pigment of the present invention, can be used alone or as a mixture titanium oxide, zinc sulphide, zinc oxide, barium sulphide, potassium titanate etc., wherein, preferential oxidation titanium.The content of white pigment is preferably 5～200 mass parts with respect to polymethylpentene resin 100 mass parts, more preferably 10～150 mass parts, more preferably 20～80 mass parts.
With regard to the median size of white pigment, consider plasticity and consider from obtaining the viewpoint of high-reflectivity, preferably primary particle size is distributed as 0.10～0.50 μ m, more preferably 0.10～0.40 μ m, more preferably 0.21～0.25 μ m.Median size can be with by utilizing the mass average value D50 form that the particle size distribution of laser diffractometry obtains to try to achieve.
About spheroidal fused silicon dioxide granule of the present invention and special crosssection glass fibre, conventionally be engaged in the such hot curing resin composition of thermoplastic resin composition and epoxy resin, acrylic resin, silicone resin, the goods that obtain can be used alone or mix use.
At this, " spherical " of " so-called spheroidal fused silicon dioxide granule " do not refer to the shape such as laminar of shape that so fibrous, the concavo-convex difference of glass fibre is large, thin thickness, and the shape that to refer to from the center to surperficial ultimate range and minor increment be same degree, particularly, refer to that following average spherical degree is more than 0.8 subsphaeroidal or spherical.By being the shape such as subsphaeroidal or spherical, there is no anisotropy, can highly fill, and the mobility in mould, resistant to mold wear etc. are also excellent.
Above-mentioned average spherical degree for example can be measured by the particle picture that utilizes NEC company scanning electron microscope processed " FE-SEM, type JSM-6301F " to take is carried out to image analysis.That is, by photo, measured shadow area (A) and the girth (PM) of particle.If the area of the proper circle corresponding to girth (PM) is made as to (B), the out of roundness of this particle can be expressed as A/B.Therefore, if imagination has the proper circle with girth (PM) same circumference of sample particle, due to PM=2 π r, B=π r 2, B=π * (PM/2 π) 2, the sphericity of each particle can be used as sphericity=A/B=A * 4 π/(PM) 2calculate.Obtain the sphericity of any 200 particles that as above obtain, its mean value is made as to the average spherical degree of powder.In addition, the average spherical degree that indicates the material of " spherical (spherical) " in common commercially available product is more than 0.8.
Spheroidal fused silicon dioxide granule is through for example following operation manufacture: in the melt region in stove, in formed flame, silicon dioxide powder powder stock (such as silica powder) is together sprayed under pulverulence from burner with carrier gas such as air.Generally speaking, can use commercially available product.
From the viewpoint of the balance of thermotolerance and plasticity, consider, the volume average particle size of spheroidal fused silicon dioxide granule is preferably 0.1～500 μ m, more preferably 1～200 μ m, more preferably 5～150 μ m.This volume average particle size can be used as the mass average value D50 utilizing in the particle size distribution that laser diffractometry obtains and tries to achieve.
In addition, so-called " special crosssection glass fibre " refers to the fiber with the minor axis in the cross section cross-sectional shape different with long-neck.Owing to strengthening about equally in resin flows direction (MD) and its vertical direction (TD), therefore, excellent aspect preventing in the warpage of molding.
In the present invention, be preferably the glass fibre of average fiber length 0.75～300 μ m with following cross-sectional shape: the minor axis D1 in cross section is that 0.5～25 μ m, major diameter D2 be 0.6～300 μ m, D2 are 1.2～30 with respect to the ratio D2/D1 of D1.This fiber footpath and staple length can be extracted the glass fibre of specified amount out randomly by the arbitrfary point from glass fiber laminate, the fiber that utilizes the pulverizing such as mortar to extract out, utilizes image processing apparatus measurement to try to achieve.
The content of spheroidal fused silicon dioxide granule and/or special crosssection glass fibre is preferably 10～300 mass parts with respect to polymethylpentene resin 100 mass parts, more preferably 30～200 mass parts, more preferably 50～120 mass parts.
Electrocuring resin combination of the present invention can be made with regulation as above at least arbitrary inorganic particulate and white pigment in above-mentioned polymethylpentene resin and crosslinking Treatment agent, spheroidal fused silicon dioxide granule, special crosssection glass fibre and other glass fibre as required than mixing.As blending means, can apply the stirrers such as two rollers or three rollers, clarifixator, planetary-type mixer, polymerization experiment system or the known devices such as melting mixing machine such as plasticity grinding machine for experiment.These carry out under arbitrary state of normal temperature, the state of cooling, heated condition, normal pressure, decompression state, pressurized state.
In addition, only otherwise damage effect of the present invention, can contain various additives.For example, in order to improve the character of resin combination, can coordinate the additives such as photostabilizer such as the antioxidants such as the internal mold releases such as various whiskers, organosilicon powder, thermoplastic elastomer, organic synthesis rubber, fatty acid ester, glycerate, Zinic stearas, calcium stearate or benzophenone, salicylic acid, cyanoacrylate, isocyanuric acid ester class, oxalic acid phenyl amines, benzoates, hindered amines, benzotriazole category, phenols or hindered amines, benzoates.
The electrocuring resin combination of the application of the invention, the various moldinies that can be shaped, also can make the molding that thickness is thinner (for example reverberator).
Such molding is preferably manufactured by manufacturing process of the present invention.That is, by comprising that the manufacturing process of following operation makes: injection molded operation, at 20～100 ℃ of 200～400 ℃ of sleeve temperature, die temperature, electrocuring resin combination of the present invention is carried out to injection molded; With electron beam irradiation operation, before or after injection molded operation, implement electron beam irradiation and process.
In addition, only otherwise infringement plasticity, can before shaping, utilize the crosslinking reaction of electron beam irradiation.
For the acceleration voltage of electron beam, can be suitable selected according to the thickness of the resin using or layer.For example, in the situation that thickness is the forming composition of 1mm left and right, conventionally preferably with acceleration voltage 250～2000kV left and right, uncured resin layer is solidified.In addition, in the irradiation of electron beam, because the higher transmission capacity of acceleration voltage more increases, therefore, in the situation that use because the deteriorated body material of electron beam is as body material, by selected acceleration voltage, make the transmission depth of electron beam equal in fact with the thickness of resin layer, can suppress the irradiation to the unnecessary electron beam of body material, can be by the deteriorated irreducible minimum that is controlled at of the body material because of excess electrons Shu Yinqi.In addition, absorbed dose during irradiating electron beam can be according to the suitable setting of the composition of resin combination, but preferably makes the saturated amount of cross-linking density of resin layer, is preferably 10～400kGy, more preferably 50～200kGy.And then, as electron beam source, be not particularly limited, such as using pause type, model of Cockcroft Wal to obtain the various electron-beam accelerators such as Greif type, resonant transformer type, insulating core transformer type or linear pattern, dynamitron type, high-frequency type.
Electrocuring resin combination of the present invention as above can be used as and is coated on body material and curing matrix material or the cured article of electrocuring resin combination are applied to various uses.For example can be used as the reverberator of light source for illumination that the light-reflecting sheet of thermotolerance insulating film, thermotolerance release sheet, thermotolerance transparent base material, solar cell or the LED of take are representative or TV.
[2. reverberator resinous framework]
Reverberator of the present invention contains the cured article that the electrocuring resin combination of the invention described above is shaped and is formed with resinous framework.Particularly, reverberator of the present invention is made of resin to particle, by injection molded, forms the resinous framework of intended shape, can manufacture thus reverberator resinous framework of the present invention.Reverberator is preferably 0.1～3.0mm with the thickness of resinous framework, more preferably 0.1～1.0mm, more preferably 0.1～0.5mm.
In electrocuring resin combination of the present invention, for example, can make the less resinous framework of resinous framework that is shaped as anisotropic glass fibre making for Thickness Ratio.Particularly, can make the resinous framework of 0.1～3.0mm thickness.In addition, even if the reverberator of the present invention that as above shaping forms reduces thickness with resinous framework, also can not produce the warpage causing because containing the anisotropic fillers such as glass fibre, therefore, morphological stability and operability are also excellent.
Reverberator of the present invention loads LED chip thereon with resinous framework, recycles known sealing agent and seals, and carries out die bonding and forms the shape of expectation, can form semiconductor light-emitting apparatus thus.In addition, reverberator of the present invention plays a role as reverberator with resinous framework, but also can be used as supporting semiconductor light-emitting apparatus framework play a role.
In addition, at reverberator of the present invention, use in resinous framework, by containing spheroidal fused silicon dioxide granule, compare with the situation of cooperation porous silica particle, owing to can suppressing the foaming that water causes in the operation manufacturing this framework, therefore, do not form the minute aperture that produces bad degree.Therefore, for example,, in using the goods (semiconductor light-emitting elements) of this framework, difficult generation results from the bad of minute aperture, therefore, can improve the weather resistance as these goods.
[3. reverberator]
Reverberator of the present invention is made by the electrocuring resin combination of the invention described above is solidified to the cured article forming.
This reverberator can be used in combination with semiconductor light-emitting apparatus described later, also can be used in combination with the semiconductor light-emitting apparatus consisting of other material (LED mounting substrate).
Reverberator of the present invention mainly has the effect to the direction reflection of lens (light out part) from the light of the LED element of semiconductor light-emitting apparatus that makes.For the details of reverberator, due to identical with applied reverberator in semiconductor light-emitting apparatus of the present invention (reverberator 12 described later), therefore, in this omission.
In addition, reverberator of the present invention, by containing spheroidal fused silicon dioxide granule, can suppress the foaming that water causes in the operation of manufacturing this reverberator, does not therefore form the minute aperture that produces bad degree.Therefore, for example,, in using the goods (semiconductor light-emitting elements) of this reverberator, difficult generation results from the bad of minute aperture, therefore, can improve the weather resistance as these goods.
As mentioned above, the electrocuring resin combination that use contains spheroidal fused silicon dioxide granule has formed the semiconductor light-emitting elements of reverberator owing to not forming the minute aperture that produces bad degree in this reverberator, therefore, difficult generation results from the bad of minute aperture.Therefore, improve the weather resistance as these goods.
[4. semiconductor light-emitting apparatus]
Semiconductor light-emitting apparatus of the present invention, as illustrated in Fig. 1, has optical semiconductor (for example LED element) 10 and is arranged on this optical semiconductor 10 around and make the reverberator 12 to prescribed direction from the luminous reflectance of optical semiconductor 10 on substrate 14.And at least a portion of the light reflection surface of reverberator 12 (being all the in the situation that of Fig. 1) is made by the cured article of the reflector group compound of the invention described above.
Optical semiconductor 10 is for having the semi-conductor chip (twinkler) that sends radiating light (being UV or blue light conventionally) in white light LED, it has the double-heterostructure that for example utilizes the coating layer of N-shaped and p-type to clamp the active coating consisting of AlGaAs, AlGaInP, GaP or GaN, for a for example edge lengths is the hexahedral shape of 0.5mm left and right.And, in the situation that metal wire engage to be installed, by going between, 16 be connected with not shown electrode (splicing ear).
The shape of reverberator 12 is according to end (junction surface) shape of lens 18, is generally tubular or the colyliform such as square, circular, oval.In the summary sectional view of Fig. 1, reverberator 12 is cylindrical body (wheel-shaped body), whole end faces of reverberator 12 and the Surface Contact of substrate 14, fixing.
In addition, in order to improve the directive property from the light of optical semiconductor 10, the inner face of reverberator 12 also can be expanded into taper (with reference to Fig. 1) up.
In addition, reverberator 12 in the situation that the shape corresponding to these lens 18 is processed into in the end of lens 18 sides, also can be used as lens carrier and plays a role.
Reverberator 12 as shown in Figure 2, also can only make the reflection layer 12a of light reflection surface side for being made by electrocuring resin combination of the present invention.Now, from reducing the viewpoints such as thermal resistance, consider, the thickness of reflection layer 12a is preferably made as below 500 μ m, is more preferably made as below 300 μ m.The parts 12b that is formed with reflection layer 12a can be made by known heat-resistant resin.
As mentioned above, on reverberator 12, be provided with lens 18, but it typically is resin, according to object, purposes etc., adopt various structures, be also sometimes colored.
The spatial portion being formed by substrate 14, reverberator 12 and lens 18 can be transparent sealing portion, can be also space part as required.This spatial portion is generally the transparent sealing portion that is filled with the material etc. of giving light transmission and insulativity, can prevent in metal wire engage to be installed due to because 16 directly contacting the power applying and the vibration indirectly applying, impact etc. with going between, make to go between 16 from the connection section with optical semiconductor 10 and/or the electric unfavorable condition that produces with connection section disengaging, cut-out or the short circuit of electrode.In addition, can protect optical semiconductor 10 not to be subject to the impact of moisture, dust etc., can keep for a long time reliability simultaneously.
As the material (transparent sealant composition) of giving this light transmission and insulativity, conventionally can enumerate: silicone resin, epoxy silicone resin, redix, acrylic resin, polyimide based resin, polycarbonate resin etc.Wherein, from the viewpoint of thermotolerance, weathering resistance, low-shrinkage and discoloration-resistant, consider, preferably silicone resin.
Below, the manufacture method of the semiconductor light-emitting apparatus shown in Fig. 1 example is described.
First, the transfer shaping, compression molding, injection molded etc. of mould that possesses the die cavity space of regulation shape by use is configured as the reflecting material resin combination of the invention described above the reverberator 12 of regulation shape.Then, utilize caking agent or attachment that the optical semiconductor 10 of preparing separately, electrode and lead-in wire 16 are fixed on to substrate 14, then reverberator 12 is fixed on substrate 14.Then, at the recess that formed by substrate 14 and reverberator 12, inject the transparent sealant composition that contains silicone resin etc., by heating, dry etc., it is solidified, form transparent sealing portion.Then, in transparent sealing portion, set lens 18, obtain the semiconductor light-emitting apparatus shown in Fig. 1.
In addition, also can under the uncured state of transparent sealant composition, load after lens 18, composition is solidified.
Embodiment
Then, utilize embodiment to describe in further detail the present invention, but the present invention is not subject to any restriction of these examples.
It should be noted that, the material using in the present embodiment 1～15 and comparative example 1～12 is as described below.
(A) resin
Polymethylpentene resin: TPX RT18 (Mitsui Chemicals (strain) system, molecular weight: MW50 ten thousand～600,000)
Cyclopolyolefin copolymer resin: COC APL6015 (145 ℃ of Mitsui Chemicals (strain) system, second-order transition temperatures)
Polybutylene terephthalate resin: Novaduran 5008 (224 ℃ of Mitsubishi's engineering plastics (strain) systems, intrinsic viscosity [η]=0.9dl/g, melt temperature)
(B) crosslinking Treatment agent
Crosslinking Treatment agent is as described below.In addition, for the specific material of structure in following crosslinking Treatment agent, following table 1-1,1-2 and chemical formula are shown in following.
Hand over 1:DAP monomer (Phthalic acid, diallyl ester) Daiso company system
Hand over 2:DAP 100 monomers (diallyl isophthalate) Daiso company system
Hand over 3:TAIC (triallyl isocyanurate) Japan to change into company's system
Hand over 4:MeDAIC (methyl diallyl isocyanuric acid ester) four countries to change into company's system
Hand over 5:DA-MGIC (diallyl list glycidyl isocyanuric acid) four countries to change into company's system
Hand over 6:MA-DGIC (monoene propyl group diglycidyl isocyanuric acid ester) four countries to change into company's system
Hand over 7:TMAIC (isocyanuric acid trimethylammonium allyl ester) Japan to change into company's system
Hand over 8:RICON153 (polyhutadiene) Sartomer company system
Hand over 9:RICON154 (polyhutadiene) Sartomer company system
Hand over 10:RICON157 (polyhutadiene) Sartomer company system
Hand over 11:TAIC prepolymer (triallyl isocyanurate prepolymer) Japan to change into company's system
Hand over 12:TEPIC (1,3,5-triglycidyl group isocyanuric acid) daily output chemical company system
Hand over 13:TEPIC-PAS (mixture of 1,3,5-triglycidyl group isocyanuric acid and Tetra hydro Phthalic anhydride) daily output chemical company system
Hand over 14: vinylformic acid 1,3,5-tri-(2-carboxy ethyl) isocyanuric acid ester
Hand over 15:M315 (isocyanuric acid EO modification triacrylate) East Asia Synesis Company system
Hand over the Japanese chemical drug system of 16:DPHA (dipentaerythritol acrylate)
[table 1]
Table 1-1
[table 2]
Table 1-2
Formula (1)～(4) that represent the structure in table 1-1 and table 1-2 are as described below.
(C) inorganic particulate
Special crosssection glass fibre: CSG3PA-820 ((strain) system, staple length 3mm are spun in day east)
(D) white pigment
Titanium particles: PF-691 (the former industry of stone (strain) rutile-type structure median size 0.21 μ m processed)
(E) additive
Silane coupling agent: KBM-303 (SHIN-ETSU HANTOTAI's chemistry (strain) system)
Releasing agent: SZ-2000 (boundary's chemistry (strain) system)
Antioxidant: IRGANOX1010 (BASF Japan (strain) system)
Processing stabilizers: IRGAFOS168 (BASF Japan (strain) system)
[embodiment 1～15, comparative example 1～12]
As shown in table 2, table 3, table 4, cooperation, mixing various materials, obtain resin combination.In addition, mixingly with polymerization experiment system (batch-type twin shaft), carry out.
For these compositions, under 250 ℃, 30 seconds, the condition of 20MPa, press forming is 750mm * 750mm * thickness 0.2mm, is made into body.
Making acceleration voltage is 250kV, with the absorbed dose stipulated to this molding irradiating electron beam.Following all characteristics to them are evaluated.Show the result in following table 2, table 3, table 4.
(evaluating 1)
Storage modulus
Utilize RSAIII (TA INSTRUMENTS system), under the condition that is 0.1% at 25～300 ℃ of temperature of mensuration, 5 ℃/min of heat-up rate, Strain, measure the sample after being shaped.Storage modulus at 260 ℃ is shown in to following table 2 and table 3.
(evaluating 2)
Reflow Soldering is heat-resisting
Making the sample after sample after being shaped makes to be shaped by the small-sized nitrogen atmosphere reflow soldering apparatus RN-S (SUNX system) setting is at 260 ℃, to keep 10 seconds in the top temperature of specimen surface, by size changing rate (velocity of variation and horizontal velocity of variation sum longitudinally) evaluation, has or not distortion.Show the result in following table 4.
(evaluating 3)
Long-term heat resistance
Sample after being shaped is placed before 24 hours, 500 hours at 150 ℃ and afterwards, used spectrophotometer UV-2550 (Shimadzu Seisakusho Ltd.'s system) to measure the luminous reflectance factor of wavelength 230～780nm.By the table 4 that the results are shown in of wavelength 450nm.
According to table 2 and table 3, resin combination of the present invention is by carrying out electron beam irradiation under the existence in specific crosslinking Treatment agent, even can melting in high-temperature region yet, and can be in the hope of storage modulus.Can confirm thus, by carrying out electron beam irradiation under the existence in specific crosslinking Treatment agent, to carry out effective crosslinking reaction.
By table 3, can confirm to follow the amount of crosslinking Treatment agent, the increase of electron beam irradiation amount, storage modulus also increases.Can confirm that thus degree of crosslinking depends on the amount of crosslinking Treatment agent, electron beam irradiation amount.
In addition, in the situation that be only the resin combination of resin and crosslinking Treatment agent, if the amount of crosslinking Treatment agent increases, find that there is the tendency that is difficult to press forming, but by coordinate inorganic particulate or white pigment in this resin combination, can compression moulding.
In addition, by table 4, can be confirmed to use in resin combination in the reflection through electron beam irradiation, the change in shape causing because of Reflow Soldering test also significantly alleviates.In addition, can confirm that long-term heat resistance is excellent.If particularly compare the result of the diverse embodiment 15 of resin, comparative example 11 and comparative example 12, the dimensional stability of known embodiment 15 and long-term heat resistance are the most excellent.
According to above content, the reflecting material that resin combination of the present invention is used for reverberator or semiconductor light-emitting apparatus is useful.

Claims (14)

1. an electrocuring resin combination, it contains polymethylpentene and crosslinking Treatment agent,
Described crosslinking Treatment agent has saturated or undersaturated ring structure, and the arbitrary allyl class substituting group bonding in the methacrylic that forms at least 1 atom in the atom of at least 1 ring and allyl group, methacrylic, the allyl group being connected by linking group and connect by linking group, the molecular weight of described crosslinking Treatment agent is below 1000.
2. electrocuring resin combination according to claim 1, wherein, form at least 2 atoms in the atom of 1 ring of described crosslinking Treatment agent respectively independently with described allyl class substituting group bonding.
3. electrocuring resin combination according to claim 2, wherein, the ring of described crosslinking Treatment agent is 6 rings, and form at least 2 atoms in the atom of this ring respectively independently with described allyl class substituting group bonding, with respect to bonding, there is 1 substituent atom of allyl class, other allyl class substituting group and a position atomic linkage.
4. according to the electrocuring resin combination described in any one in claim 1～3, wherein, described crosslinking Treatment agent represents by following formula (1),
In formula (1), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.
5. according to the electrocuring resin combination described in any one in claim 1～3, wherein, described crosslinking Treatment agent represents by following formula (2),
In formula (2), R 1～R 3be respectively the arbitrary allyl class substituting group in allyl group, methacrylic, the allyl group connecting by ester bond and the methacrylic that connects by ester bond independently.
6. according to the electrocuring resin combination described in any one in claim 1～5, wherein, with respect to polymethylpentene 100 mass parts, be combined with the described crosslinking Treatment agent of 0.1～15 mass parts.
7. according to the electrocuring resin combination described in any one in claim 1～6, it contains white pigment.
8. electrocuring resin combination according to claim 7, it contains the inorganic particulate beyond described white pigment.
9. electrocuring resin combination according to claim 8, wherein, the inorganic particulate beyond described white pigment is spheroidal fused silicon dioxide granule and/or special crosssection glass fibre.
10. a reverberator resinous framework, the cured article that it contains the electrocuring resin combination described in any one in claim 1～9.
11. reverberator resinous frameworks according to claim 10, its thickness is 0.1～3.0mm.
12. 1 kinds of reverberators, its cured article by the electrocuring resin combination described in any one in claim 1～9 is made.
13. 1 kinds of semiconductor light-emitting apparatus, it has optical semiconductor and reverberator on substrate, described reverberator is arranged at this optical semiconductor around, and by the luminous reflectance from this optical semiconductor to prescribed direction,
At least a portion of the light reflection surface of described reverberator is made by the cured article of the electrocuring resin combination described in any one in claim 1～9.
The manufacture method of 14. 1 kinds of moldinies, it comprises: injection molded operation, at 20～100 ℃ of 200～400 ℃ of injection temperatures, die temperature, the electrocuring resin combination described in any one in claim 1～9 is carried out to injection molded; With electron beam irradiation operation, before or after injection molded operation, implement electron beam irradiation and process.
CN201380014798.9A 2012-01-17 2013-01-17 Electron beam curable resin composition, resin frame for reflectors, reflector, semiconductor light emitting device, and method for producing molded body Pending CN104169359A (en)

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